5

Heat Treatment Processes for Steels

Treatment

INTRODUCTION

The area of application for any metal or alloy is limited by its properties. These properties can
be varied within limits by several methods, namely, mechanical working, alloying, grain size
control and heat treatment. The importance of heat treatment has been dealt with in Chapter 1.
Heat treatment affects mechanical properties either by allotropic transformation or by changing
relative solubilities of element(s) in the base metal. The theory of allotropic transformation,
generally encountered in ferrous metals, has already been discussed in Chapter 4. Heat treatment
practices for commercial steels are discussed in Chapter 14. (The theory and practice of heat
treatment for non-ferrous metals and alloys are dealt with in Chapter 16.) Steel is the most
important and versatile engineering alloy. It finds numerous applications. Heat treatment plays
an important role in such a wide acceptance of steel as an engineering material. Properties of
steel can be controlled and varied over a very wide range by heat treatment. Thus, a thorough
understanding of heat treatment of steel is very important. In the sections that follow, we
discuss various heat treatment processes.

5.1 STRESS RELIEVING

As the name suggests, this process is employed to relieve internal stresses. No microstructural
changes occur during the process. In this sense, it differs from other subcritical treatments in
which structural improvement takes place. Internal stresses are those stresses which can exist
within a body in the absence of external forces. These are also known as residual stresses or
locked-in stresses. Internal stresses are developed during different operations like solidification
of castings, welding, machining, grinding, shot peening, surface hammering, cold working,
case hardening, electroplated coatings, precipitation and phase transformation. Internal stresses
under certain conditions can have adverse effects. For example, steels with residual stresses
under corrosive environment fail by stress-corrosion cracking, whereas, in general, failure by
stress-corrosion cracking occurs under the combined action of corrosion and externally applied
stresses. These stresses also enhance the tendency of steels towards warpage and dimensional
instability. Fatigue strength is reduced considerably when residual tensile stresses are present

86
 Heat Treatment Processes for Steels 87

in the steel. The problems associated with internal stresses are more difficult in brittle materials
than in ductile materials.
The process of stress relieving consists of heating steel uniformly to a temperature below
the lower critical temperature, holding at this temperature for sufficient time, followed by
uniform cooling. Uniform cooling is of utmost importance as non-uniform cooling will itself
result in the development of internal stresses. Thus the very purpose of stress relieving will
be lost. For plain carbon steels and low alloy steels, maximum stress relieving temperature is
generally limited to about 600°C. Higher temperatures are employed for high alloy steels.
Hardened and tempered steels, if service conditions demand, can be stress relieved by heating
up to a temperature which is lower than tempering temperature by 25–30°C. The extent to
which stresses can be relieved depend on the temperature employed and holding time.

5.2 ANNEALING

Annealing, in general, involves heating to a predetermined temperature, holding at this

temperature, and finally cooling at a very slow rate. The temperature, to which steel is heated,
and the holding time are determined by various factors such as the chemical composition of
steel, size and shape of steel component and final properties desired. Annealing can form
either the final treatment or a preparatory step for further treatment. The various purposes of
this treatment are to (i) relieve internal stresses developed during solidification, machining,
forging, rolling or welding; (ii) improve or restore ductility and toughness; (iii) enhance
machinability; (iv) eliminate chemical non-uniformity; (v) refine grain size; and (vi) reduce the
gaseous contents in steel.
Annealing treatment can be classified into groups, based on temperature of treatment,
phase transformation that takes place during treatment, and the purpose of the treatment. All
the groups based on these three criteria are interrelated.
Depending on heat treatment temperature, annealing treatment can be subdivided into
three classes, namely, full annealing, partial annealing and subcritical annealing. For full
annealing, steel is heated above the upper critical temperature (A3) and then cooled very
slowly. Partial annealing, also known as incomplete annealing or intercritical annealing, involves
heating of steel to a temperature lying between lower critical temperature (A1) and upper
critical temperature (A3 or Acm). The steel may be cooled very slowly from the annealing
temperature, or it may be cooled in air from a temperature at which or above which all the
austenite has been transformed into pearlite. Subcritical annealing, as the name suggests, is a
process in which the maximum temperature to which steel is heated is always less than the
lower critical temperature (A1). These processes have been represented in Figure 5.1. In
subcritical annealing, no phase transformation takes place. Only thermally activated phenomena,
such as recovery, recrystallization, grain growth, agglomeration of carbide and softening occur
in this process. The rate of cooling from a subcritical temperature is of little significance since
practically there is no variation as far as microstructure and final properties are concerned.
On the basis of phase transformation features, annealing can be of two types. The first type
or first-order annealing is associated with a peculiar characteristic that heat treatment is
performed on the steel with the sole aim of achieving some properties. As such, no specific
importance is given to phase transformation accompanying the treatment. In other words, any
88 Heat Treatment—Principles and Techniques

Figure 5.1 Various types of annealing processes classified on the basis of annealing temperature.

change in the characteristics of steel achieved by this type of annealing is not correlated to
phase transformation. This is the reason why a wide range of temperature is available for this
type of annealing. It can be performed at a wide range of temperatures above or below the
critical temperatures. The second type or second-order annealing differs from the first type in
the sense that the end results in the former are essentially due to phase transformation which
takes place during the treatment. For this reason, the temperature range for this treatment is
restricted as compared to the first type. Only temperatures above the upper and lower critical
temperatures can be utilized for this type of annealing.
Depending on the specific purpose, annealing is classified into various types, e.g. diffusion
annealing, spheroidizing annealing, full annealing and recrystallization annealing. The prefix
with the word annealing describes the basic purpose of the type of annealing. Various annealing
processes are discussed in the following sections.

5.2.1 Full Annealing

The term annealing, until and unless specified, means full annealing. It consists of heating
steel to austenitic region, followed by slow cooling. Steel is heated to about 30–50°C above
the upper critical temperature (A3) for hypoeutectoid steels. The steel is held at this temperature
for predetermined time, followed by cooling at a very slow rate such as cooling in the furnace
itself or in a container made of a heat insulating material. Due to such a slow cooling rate,
equilibrium structures as predicted by equilibrium diagram are obtained in the steel. The steel
is heated above the upper critical temperature in order to get a homogeneous austenitic structure.
Alloy steels, specially those containing strong carbide forming elements, need higher
annealing temperatures than plain carbon steels and other alloy steels. The upper limit of
holding temperature is generally restricted to Ac3 + 50°C in order to check grain coarsening.
Steel will become very soft after this treatment. Since a completely austenitic structure can be
obtained by heating eutectoid steel above the lower critical temperature (A1), eutectoid steel
is heated 30–50°C above the lower critical temperature for full annealing treatment. This
treatment results in a structure consisting of lamellar pearlite. The interlamellar spacing will
 Heat Treatment Processes for Steels 89

depend mainly on the annealing temperature and the cooling rate. This process, in general, is
not employed for hypereutectoid steels. The reason for this is that heating above the upper
critical temperature Acm followed by slow cooling will result in considerable coarsening of
austenitic grains, formation of coarse lamellar pearlite and network of cementite on the grain
boundary. Neither coarse pearlite nor cementite network at grain boundaries is desirable. Such
a structure has inherent brittleness and poor mechanical properties. The objective of the
treatment is to improve ductility, remove internal stresses completely, get enhanced magnetic
and electrical properties, and refine the grain structure. The austenitic grain size is minimum
just above the upper critical temperature (A3) for hypoeutectoid steels and above the lower
critical temperature (A1) for eutectoid steel. This treatment improves the machinability of
medium carbon steels to a great extent. Almost all castings, rolled stocks and forgings are
subjected to this treatment in order to attain enhanced mechanical properties by refinement of
grains and transformation of dendrites to equiaxed grains and elimination of segregated zones.
The prolonged heat treatment cycle, involved in this process, makes it quite expensive. This
is one of the main drawbacks associated with this process.

5.2.2 Isothermal Annealing

In this process, hypoeutectoid steel is heated above the upper critical temperature (A3) and
held for some time at this temperature. This is done in order to get a completely austenitic
structure and to eliminate any temperature gradient within the steel component. The steel is
then cooled rapidly to a temperature less than the lower critical temperature (A1). This
temperature is usually chosen between 600°C and 700°C. Fast cooling can be achieved by
rapidly transferring steel to another furnace maintained at the desired temperature. The required
temperature is one at which supercooled austenite has minimum stability within the pearlitic
region. The steel is held at this temperature till all the austenite gets transformed to pearlite.
After all the austenite is transformed into lamellar pearlite, steel is cooled in air. In fact,
cooling rates from this temperature are immaterial as no further transformation will take place.
However, the magnitude of internal stresses developed within the steel will vary with cooling
rate. The prefix “isothermal” associated with annealing implies that transformation of austenite
takes place at a constant temperature. For all practical purposes, the microstructure is equivalent
to that obtained by full annealing. The major advantage of this process over full annealing is
that the time required for heat treatment cycle is cut short to a considerable extent. Shorter heat
treatment cycle makes the process cheaper than full annealing process. The eutectoid steel is
first heated to above A1 temperature, and then it is rapidly cooled to a temperature lower than
A1. Steel is held at this temperature till austenite to pearlite transformation is complete. Finally,
steel is cooled in air. Hypereutectoid steel is, in general, not subjected to this treatment. The
reason for it is the same as discussed for full annealing. Thus, isothermal annealing can be
viewed as modified full annealing process. It results in more homogeneous structure as
transformation takes place at a constant temperature throughout the steel.
This process not only improves machinability in general, but also results in a better surface
finish by machining. The process is of great use for alloy steels as these steels have to be
cooled slowly. However, it has one important limitation. It is suitable only for small-sized
components. Heavy components cannot be subjected to this treatment because it is not possible
to cool them rapidly and uniformly to the holding temperature at which transformation occurs.
90 Heat Treatment—Principles and Techniques

For this reason, structure will not be homogeneous and mechanical properties will vary across
the cross-section. Figure 5.2 represents heat treatment cycle for isothermal annealing.

Figure 5.2 Heat treatment cycle for isothermal annealing of (a) hypoeutectoid steel and
(b) eutectoid steel.

5.2.3 Diffusion Annealing

This process, also known as homogenizing annealing, is employed to remove any structural
non-uniformity. Dendrites, columnar grains and chemical inhomogeneities are generally
observed in the case of ingots, heavy plain carbon steel casting, and high alloy steel castings.
These defects promote brittleness and reduce ductility and toughness of steel. In diffusion
annealing treatment, steel is heated sufficiently above the upper critical temperature
(say, 1000–1200°C), and is held at this temperature for prolonged periods, usually 10–20 hours,
followed by slow cooling. Segregated zones are eliminated, and a chemically homogeneous
steel is obtained by this treatment as a result of diffusion. Heating to such a high temperature
results in considerable coarsening of austenitic grains and heavy scale formation. The coarse
austenite thus obtained further transforms to coarse pearlite on cooling, which is not a desirable
structure as mechanical properties are impaired.
The coarse grained structure can be refined either by plastic working for ingots or by
employing a second heat treatment for castings. Hypoeutectoid and eutectoid steel castings are
given full annealing treatment, whereas hypereutectoid steel castings are either normalized or
partially annealed for this purpose. Scaling results in loss of metal and, therefore, heating is
done in a controlled manner and the temperature is so chosen that holding time is minimized.
Higher temperatures, longer holding periods, slow cooling rates, excessive scaling, and necessity
for a second heat treatment make this process highly expensive.

5.2.4 Partial Annealing

Partial annealing is also referred to as intercritical annealing or incomplete annealing. In this
process, steel is heated between the lower critical temperature (A1) and the upper critical
temperature (A3 or Acm). It is followed by slow cooling. Generally, hypereutectoid steels are
 Heat Treatment Processes for Steels 91

subjected to this treatment. The resultant microstructure consists of fine pearlite and cementite
instead of coarse pearlite and a network of cementite at grain boundaries, as observed in the
case of full annealing. The reason for this is that grain refinement takes place at a temperature
of about 10 to 30°C above Ac1 for hypereutectoid steels. As low temperatures are involved
in this process, it is less expensive than full annealing which involves higher temperatures.
Hypoeutectoid steels are also subjected to this treatment in order to improve their machinability.
However, all hypoeutectoid steels cannot be given this treatment. Steels with coarse structure
of ferrite and pearlite or with widmanstätten structure are not suitable for this treatment. This
is so because only partial phase transformation takes place in this process. A considerable
amount of ferrite remains untransformed, and only a part of it along with pearlite transforms
to austenite. This coarse or accicular untransformed ferrite results in poor mechanical properties.

5.2.5 Recrystallization Annealing

Practically all steels, which have been heavily cold worked, are subjected to this treatment.
The process consists of heating steel above the recrystallization temperature, holding at this
temperature and cooling thereafter. It results in decrease in hardness or strength and increase
in ductility. The desired extent of reduction in cross-sectional area is possible with the adoption
of cold-work-recrystallization anneal cycle(s). The process is used both as an intermediate
operation and as a final treatment. The treatment is very important and is frequently employed
in industries manufacturing steel wires, sheets and strips. The final structure, after the treatment,
consists of strain-free grains produced at the expense of deformed original grains. The
temperature for recrystallization annealing is not fixed, as is the case with other annealing
processes such as full annealing or process annealing. Recrystallization temperature, and also
recrystallization annealing temperature, depends on chemical composition, amount of prior
deformation, holding time and initial grain size. A minimum amount of deformation is essential
to cause recrystallization. The amount of deformation should be such that sufficient number
of lattice defects are developed in the crystal. These defects initiate the nucleation for the
production of new grains. The larger the degree of deformation, the lower is the recrystallization
temperature. Recrystallization can be achieved at lower temperatures by increasing the holding
time. However, the effect of temperature is more predominant than that of holding time. So,
it is always desirable to raise recrystallization temperature instead of increasing holding time.
A fine structure can be developed in the steel by deforming it heavily and heating to a
temperature just above the recrystallization temperature. High carbon steels and alloy steels
require higher recrystallization temperatures. The process may also result in the agglomeration
of carbide particles.

5.2.6 Process Annealing

In this treatment, steel is heated to a temperature below the lower critical temperature, and is
held at this temperature for sufficient time and then cooled. Since it is a subcritical annealing,
cooling rate is of little importance. The purpose of this treatment is to reduce hardness and to
increase ductility of cold-worked steel so that further working may be carried out easily. It is
an intermediate operation and is sometimes referred to as in-process annealing. The process
is less expensive than recrystallization annealing. It differs from recrystallization annealing in
92 Heat Treatment—Principles and Techniques

the sense that complete recrystallization of cold-worked steel may or may not take place in
this treatment. Parts which are fabricated by cold forming such as stamping, extrusion,
upsetting and drawing are frequently given this treatment as an intermediate step(s). The
heating temperatures for various annealing treatments are shown in Figure 5.3.

Figure 5.3 Temperature ranges for various types of annealing processes.

5.3 SPHEROIDIZING

Spheroidizing is a heat treatment process which results in a structure consisting of globules or

spheroids of carbide in a matrix of ferrite. In other words, ceroentite of lamellar pearlite in the
case of hypoeutectoid and eutectoid steels, and both lamellar and free cementite in the case
of hyper-eutectoid steels, coalesce into tiny spheroids. The degree of spheroidization depends
on heat treatment temperature and holding time. The process can be completed in short time
by increasing the treatment temperature. However, selection of proper temperature is very
important. With high spheroidization temperatures, dissolved carbide particles can reappear as
lamellae during cooling.
Various methods are available to obtain a spheroidized structure. One such method consists
of heating steel to a temperature just below the lower critical temperature, holding at this
temperature for prolonged periods, followed by slow cooling. Another method involves heating
and cooling steel alternately just above and below the lower critical temperature. Isothermal
annealing can also be employed for this purpose in order to save time and energy. It consists
of heating of steel to a temperature above the lower critical temperature, followed by slow
cooling to a temperature below the lower critical temperature, and holding at this temperature
for a period till the shape of all carbide particles changes into spheroids.
 Heat Treatment Processes for Steels 93

The spheroidizing treatment is also carried out by heating steel above the lower critical
temperature. This results in a completely spheroidized structure. The extent to which steel is
to be heated above the lower critical temperature depends on the chemical composition of
steel. Eutectoid steels are heated to about 20–30°C above the lower critical temperature,
whereas hypereutectoid steels are heated 30–50°C above the lower critical temperature.
Hypereutectoid alloy steels require still higher temperatures. Medium carbon steels can be
spheroidized either by heating just above or below the lower critical temperature.
High carbon steels and alloy steels are frequently spheroidized in order to improve
machinability and ductility. Low carbon steels are not generally spheroidized. However, the
aim is to make these steels suitable for severe deformation in case they are spheroidized. Low
carbon steels, on spheroidization, become very soft and gummy (sticky). Spheroidization of
these steels does not therefore improve their machinability.
It has been observed that fine lamellar pearlite coalesces more easily than coarse pearlite.
Very fine pearlite spheroidizes still more readily. Quenched structures, consisting of fine and
well dispersed carbide phase, show greatest spheroidization rates. This means that finely
distributed carbide phase is best suited for such a treatment. Cold working of steel, prior to
the treatment also helps in accelerating the rate of spheroidization.
In certain cases, a preheat treatment is necessary. For example, a network of carbide at
grain boundaries is present in annealed hypereutectoid steel microstructure [Figure 5.4(a)].
Such a steel is first normalized in order to eliminate carbide network and then spheroidized.
Spheroidized structure is shown in Figure 5.4(b). Similarly, a very coarse structure is to be
modified so as to have finer structure (by normalizing) prior to spheroidization.

(a) Annealed (with network of cementite), ×800 (b) Spheroidized (with cementite in form of
spheroids), ×800

Figure 5.4 Hypereutectoid steel.

94 Heat Treatment—Principles and Techniques

5.4 NORMALIZING

Normalizing is a process of heating steel

(Figure 5.5) to about 40–50°C above upper
critical temperature (A3 or Acm), holding for
proper time, and then cooling in still air or
slightly agitated air to room temperature. In
special cases, cooling rate can be controlled
either by changing air temperature or air
volume. After normalizing, the resultant
microstructure should be pearlitic. This is
particularly important for some alloy steels
which are air hardening (martensite forms
on air cooling) by nature. For such steels,
cooling in air does not lead to normalized
structure. Slower cooling rates are required.
Since the temperature involved in this Figure 5.5 Temperature ranges for normalizing
and hardening treatment of steels.
process is more than that for annealing, the
homogeneity of austenite increases and it
results in better dispersion of ferrite and cementite in the final structure. This dispersion results
in enhanced mechanical properties. The grain size is finer in normalized structure than in
annealed structure. Grain size of normalized steel is governed by section thickness. As cooling
rates differ considerably from case to core, there is variation in grain size of normalized steel
over its cross-section. Refinement of grain size is one of the most important objectives of
normalizing and it is, to a great extent, practised commercially. Rolled and forged steels,
possessing coarse grains, due to high temperatures involved in these operations, are subjected
to normalizing treatment for grain refinement.
Another important application of this process is its adoption as post treatment after achieving
a homogeneous structure. Generally, heavy castings, including ingots, suffer from chemical
inhomogeneity. For its elimination, steel is heated to a temperature which is higher than that
recommended for normalizing. The casting is held for sufficient period of time so that chemical
homogeneity is achieved by diffusion. It is then followed by air cooling. In fact, cooling rates
are not of much importance in this case because the treatment is generally followed by a second
cycle of treatment. The aim of the second heat treatment cycle is to refine the coarse grained
structure developed to high temperature heat treatment. Refining is done by normalizing steel
at lower temperature. Some internal stresses are developed in these heavy castings/ingots
because of large section thickness which results in variation in cooling rates from case to core.
Normalized steels are generally stronger and harder than fully annealed steels.
Correspondingly, the machinability of steels shows an improvement on normalizing. Steels are
soft in annealed condition and tend to stick during machining. By normalizing, an optimum
combination of strength and softness is achieved, which results in satisfactory level of
machinability in steels. This method of improving machinability is specially applicable to
hypoeutectoid steel. It has been observed that carbide gets precipitated at grain boundaries and
forms continuous network, particularly in hypereutectoid steel by annealing. Normalizing is a
 Heat Treatment Processes for Steels 95

very effective process to eliminate this carbide network. Such a network is quite stable, and
not eliminated by annealing treatment since there is reprecipitation during cooling. Due to the
shorter time available during cooling, this network does not appear in normalized structure.
Normalizing treatment is frequently applied to steels in order to achieve any one or more of
the objectives, namely, grain refinement, improvement in machinability, and enhanced
mechanical properties such as hardness, strength and toughness.

5.4.1 Normalizing versus Annealing

Normalized steels are harder than annealed ones. Relatively rapid cooling in the case of
normalizing results in higher degree of supercooling. Therefore, austenite decomposes at
relatively lower temperatures, resulting in better dispersion of ferrite-carbide aggregate. Also,
the amount, of pearlite is more. Both of these factors result in higher strength and hardness.
So, where these properties are desired, annealing treatment cannot be employed, and
normalizing should be done. Prolonged heat treatment time and higher energy consumption
make the annealing treatment more expensive than normalizing. Thus, normalizing is the
preferred treatment in industries. Cooling rates are not critical for normalizing as in the case
of annealing. They can be increased considerably in order to cut short the total time for
treatment. The only point to be considered is that cooling should result only in production of
equilibrium microconstituents. After a particular temperature is attained, which is well below
the lower critical temperature, steel may be quenched. Normalized steel has lower impact
transition temperature than annealed steel. This is essentially due to the finer grain size of
normalized steel. Annealing improves the machinability of medium carbon steels, whereas
normalizing improves machinability of low carbon steels.

5.5 HARDENING
Certain applications demand high tensile strength and hardness values so that the components
may be successfully used for heavy duty purposes. High tensile strength and hardness values
can be obtained by a process known as hardening. Hardening treatment consists of heating to
a predetermined temperature, usually known as hardening temperature (see Figure 5.5), holding
at that temperature, followed by rapid cooling such as quenching in water, oil or salt baths.
The high hardness developed by this process is due to the phase transformation accompanying
rapid cooling. The term rapid cooling simply does not mean that cooling rate is higher than
that adopted in annealing and normalizing. What it really means is that cooling rate is equal
to or more than the upper critical cooling rate. Rapid cooling results in the transformation of
austenite at considerably low temperatures into non-equilibrium product. The product of low
temperature transformation of austenite is martensite which is a hard microconstituent of steel.
The term hardening by quenching is used for this process in order to differentiate it from other
hardening processes.
The hardening temperature (Figure 5.5) depends on chemical composition. For plain carbon
steels, it depends on carbon content alone. Hypoeutectoid steels are heated to about 30–50°C
above the upper critical temperature, whereas eutectoid and hypereutectoid steels are heated
to about 30–50°C above the lower critical temperature. Ferrite and pearlite transform to austenite
at hardening temperature for hypoeutectoid steels. This austenite transforms to martensite on
96 Heat Treatment—Principles and Techniques

rapid quenching from hardening temperature. The presence of martensite accounts for high
hardness of quenched steel. If hypoeutectoid steel is heated to a hardening temperature
equivalent to that for hypereutectoid steel, the structure will consist of ferrite and austenite.
This will transform to ferrite and martensite on quenching. Ferrite, a very soft phase, lowers
the hardness of hardened steel considerably. Thus, the very purpose of hardening, i.e. attainment
of improved mechanical properties, is lost. This is also known as incomplete hardening, and
is not usually employed in practice. The preferred hardening temperature for hypereutectoid
steel lies between the lower critical temperature (A1) and the upper critical temperature (Acm).
The advantage gained from hardening temperature in this range is two-fold. The first is related
to the presence of cementite in hardened steel. The cementite in a martensitic matrix accounts
for several desirable properties. Wear resistance is one of them. The fact that both martensite
and cementite are hard constituents is responsible for high wear resistance of the resulting
microstructure. Cementite is harder than martensite and so wear resistance of the two-phase
microstructure is better than what is achieved by martensite alone. The second advantage of
this hardening temperature is the attainment of fine martensite in the final structure. In fact,
heating of hypereutectoid steel above the upper critical temperature (Acm) for hardening is
detrimental because such a high temperature will result in coarsening of austenitic grains and
decarburization at the surface. Coarse austenite will transform to coarse accicular martensite
(microstructure, Figure 5.6) which has poor mechanical properties. Decarburized surface
responds poorly to hardening treatment. In addition to these factors, quenching from such a
high temperature will introduce severe internal stresses into the hardened steel.

Figure 5.6 Microstructure showing coarse accicular martensite (×300).

The main purpose of hardening tool steel is to develop high hardness. This enables tool
steel to cut other metals. High hardness developed by this process also improves wear resistance.
This may be the sole aim of the process for components such as gears, shafts and bearings.
Tensile strength and yield strength are improved considerably by hardening structural steels.
In the case of structural steels, yield strength is more important than tensile strength as it
 Heat Treatment Processes for Steels 97

measures the safe limit of maximum allowable stresses. The higher the yield strength, the
greater is the magnitude of stress to which a part can be subjected in service. Since yield
strength is the limit of stress up to which elasticity is maintained, an increase in yield strength
results in increase of stress level which the material can withstand without loss of elasticity.
This is a very important property of springs.
Because of rapid cooling, high internal stresses are developed in the hardened steel.
Therefore, hardened parts are seldom used in as-hardened condition. Also, in hardened
condition, steels are generally brittle. Hardening, in general, is always followed by another
treatment known as tempering which reduces internal stresses and makes the hardened steel
relatively stable. Hardening followed by tempering results in improved wear resistance,
optimum combination of strength and ductility and enhanced elastic characteristics.

5.5.1 Factors Affecting Hardening Process

The properties of steel developed by hardening depend on various factors. Important among
these factors are (i) chemical composition of steel, (ii) size and shape of the steel part, (iii)
hardening cycle, i.e. heating rate, hardening temperature, holding time and cooling rate, (iv)
homogeneity and grain size of austenite, (v) quenching media, and (vi) surface condition of
steel part. All these factors are interrelated. In fact, these factors affect almost all heat treatment
processes and are of great importance for hardening treatment, due to rapid cooling, which
results in the transformation of austenite to non-equilibrium product.
Chemical composition of steel largely determines the hardening temperature since critical
temperature depends on it. In the case of alloy steels, the hardening temperature has to be
controlled closely, and depends on the nature and amount of alloying element(s). Comparatively
larger amount of retained austenite is present in the hardened steels containing austenite
stabilizing elements. The presence of retained austenite greatly reduces strength. The presence
of alloy carbides increases wear resistance of the hardened steel to a great extent. The reason
for this is that, in general, alloy carbides are harder than cementite. The higher the content of
carbide forming element(s) in a given alloy steel, the larger is the volume fraction of carbides
in the hardened steel and correspondingly higher is the wear resistance. Hardened alloy tool
steels having alloy carbide(s) in a martensitic matrix, apart from excellent wear resistance,
have many important characteristics such as longer tool life, increased cutting ability and
stability at elevated temperature.
Larger parts or parts with variable thickness of sections are heated at a very slow rate so
as to avoid thermal gradient between outer and inner layer or between thick and thin sections.
These parts should be held at the hardening temperature for sufficient time in order to attain
uniform temperature throughout the volume. Cooling rates should be so chosen that complete
hardening may take place with minimum of defects associated with hardening process. Sharp
corners or regions where dimensional change takes place are more prone to quench cracks or
warpage. For larger parts, martensitic transformation will not proceed simultaneously throughout
the volume. This will result in production of high magnitude of internal stresses due to volume
change (associated with austenite to martensite transformation) occuring first in the case and
then in the core.
For complete hardening, hardening temperature should be such that homogeneous austenite
with minimum grain size is produced. This is achieved by heating hypoeutectoid steel to
98 Heat Treatment—Principles and Techniques

30 to 50°C above Ac3 temperature. Eutectoid and hypereutectoid steels are heated to 30 to 50°C
above Ac1, temperature, as already explained in Section 5.5. Cooling rate equal to or greater
than the upper critical cooling rate results in complete hardening. Ideally, cooling rate should
be just equal to the upper critical cooling rate. Cooling rates more than the critical cooling rate
will simply result in development of larger internal stresses without any other advantage. This
is not desirable. Slow heating rates are desirable in some cases. However, slow heating rates
are to be avoided in cases where the problem of oxidation and decarburization is encountered.
In such cases, steel component is heated in two stages. To start with, it is heated to an
intermediate temperature which is lower than the required austenitizing temperature. The
component is soaked at this temperature for a sufficiently long time. Heating to this lower
temperature does not result in either excessive oxidation or decarburization. Now the steel part
is transferred quickly to another furnace maintained at the desired temperature. This practice
reduces the time for which steel part has been kept at high temperature. In this way, the problem
of oxidation and decarburization is minimized. Steel components which are heated to hardening
temperature at slow heating rates require less holding time for homogenization. On the other
hand, steel components or small sections which get heated up rapidly, need longer holding time.
The properties of hardened steel depend to a large extent on the nature of austenite,
because martensite in the quenched steel is formed by direct transformation of austenite.
Homogeneity and grain size of austenite play an important role as far as final properties are
concerned. A detailed discussion on this aspect is given in Section 4.9.
A desired quenching medium is one which provides a cooling rate higher than the (upper)
critical cooling rate. Quenching medium characteristics, such as its temperature, specific heat,
thermal conductivity and latent heat of vaporization, affect the cooling rate to a great extent.
The effect of these characteristics and the mechanism of heat removal from the quenching
medium are dealt with in detail in Chapter 7.
The condition of the surface of steel component also affects hardening characteristics. The
presence of oil, grease, scale and other foreign particles on the surface is not desirable. Oil and
grease burn during heating and leave behind residue which is a bad conductor of heat. Thus
the spot(s), where this residue exists, will cool at a slower rate than the rest of the surface. This
may lead to incomplete hardening. Similarly, the presence of scale or foreign particles also
results in variable cooling rates within the mass.

5.5.2 Hardening Methods

Rapid cooling is carried out in order to obtain martensite in hardened steel. Austenite to
pearlite or bainite transformation is suppressed in this process. This means that higher cooling
rates will be required only in that temperature range within which unstable austenite decomposes
to ferrite-cementite aggregate. Once this range is crossed, austenite will transform to martensite
even on slow cooling. Therefore, it is not essential to rapidly cool the steel component
throughout the complete range of temperature from hardening temperature to quenching medium
temperature. Minimum possible cooling rate will develop the lowest internal stresses in the
hardened steel. Large magnitude of internal stresses may either lead to distortion of piece or
to the formation of internal or external cracks.
Hardening can be employed on steel component in several ways, depending on quenching
procedures. Various quenching methods based on hardening are (i) conventional or direct
 Heat Treatment Processes for Steels 99

quenching, (ii) quenching in stages in sequence in different media, (iii) spray quenching,
(iv) quenching with self-tempering, (v) austempering or isothermal quenching, and
(vi) martempering (stepped quenching).
Conventional quenching is the simplest and extensively used hardening method. It consists
of quenching the steel component from hardening temperature in the quenching medium. The
part is allowed to cool up to the temperature of quenching bath. In addition to severe internal
stresses, steel parts also develop tendency towards distortion and cracking due to drastic
cooling rates involved in this process. Cooling rate can be controlled by adopting less severe
quenching media, say, oil in place of water. However, such a control has its own limitations.
Only smaller sections can be hardened in quenchants having lesser quenching power. The
process is frequently adopted for simpler shapes. Intricate shapes cannot be successfully
hardened by this process.
Quenching in stages in sequence in different media consists of quenching steel part from
hardening temperature to a bath maintained at a predetermined temperature which is higher
than the Ms temperature. The medium used, in general, is water. The part is then transferred
quickly to a milder quenching medium where it is cooled to room temperature. Oil and air are
much preferred quenching media for second quenching. Internal stresses developed in this
process are considerably less than those found in direct quenching. This is mainly due to two
reasons. Firstly, the severity of cooling is reduced. Secondly, internal stresses developed (due
to austenite to martensite transformation in stages from surface to centre) are also reduced.
Spray quenching is a specific hardening method in which the steel part is cooled rapidly
from the hardening temperature by spraying quenchant continuously. In this case, the rate of
heat extraction from the steel part is much higher as compared to direct quenching process.
The reason for this is that a continuous stream of quenchant is always in contact with the steel
surface. Thus there is no probability for formation of liquid vapour film over the steel surface.
The process is best suited for selective hardening. Water is the most commonly used quenchant
for this process.
Hardening is always followed by tempering in order to have an optimum combination of
hardness, strength and toughness. Properly hardened and tempered steel part has, in general,
uniform mechanical properties throughout the section. This condition is not desirable for all
applications. For example, certain applications, specially those involving impact loading, require
a soft and tough core with hardened and toughened case. This condition can be attained by a
process known as quenching with self-tempering. It is also referred to as time quenching. In
this process, steel part is quenched from the hardening temperature. The part is withdrawn
from the quenching bath after some time without allowing it to cool completely in the quenching
medium. In this way, considerable amount of heat will be retained in this central portion. The
component is now cooled in a mild quenching medium such as oil or air. The first quenching
results in the formation of martensite. The depth up to which martensite forms will depend to
a great extent on the time period for which the part has been allowed to remain in the
quenching bath. Cooling during second quench will result in homogenization of temperature.
The core will now be cooled at a. much reduced rate. Thus the core will undergo austenite to
pearlite transformation in place of austenite to martensite transformation. The already formed
martensite will be tempered by itself without any additional tempering treatment during second
cooling. Thus, the process results in a tough core with a hardened and toughened case.
100 Heat Treatment—Principles and Techniques

This hardening process is frequently used for chisels, sledge and hand hammers, centre
punches, shafts, collars and gears. It is also a useful process for hardening components with
intricate shapes. The only problem associated with this process is the close control of time in
the first quench. It is very difficult to know the heat contents of the piece after the first quench.
Thus it is difficult to control the tempering temperature for the martensite. Tempering
temperature cannot be measured accurately in this case. An estimation of temperature is
carried out by observing the temper colour of the surface. Hardness of tempered martensite can
be controlled by immersing the piece into water after a particular time, depending on the
temper colour of the surface. This prevents overheating of steel above the required temperature.
Isothermal quenching and stepped quenching are discussed separately in Sections 5.7 and
5.8, respectively.

5.6 TEMPERING

As mentioned in Section 5.5, hardening treatment develops maximum hardness, excellent wear
resistance and high strength levels in the steel. At the same time, it affects adversely properties
such as ductility, toughness and impact strength. It also imparts brittleness to steel because of
the internal stresses developed by quenching. The extent of brittleness depends on the chemical
composition and cooling rate. The degree of brittleness rises with increasing carbon content
and severity of cooling rate. Thus, steel in as-hardened state is unsuitable for some service
conditions and, therefore, rarely used as such. A relatively stable state can be attained by
providing thermal energy to the steel. This results in decrease in internal stresses and
reduction in the degree of brittleness. Such a process, which consists of heating hardened steel
below the lower critical temperature, followed by cooling in air or at any other desired rate,
is known as tempering.
Tempering treatment lowers hardness, strength and wear resistance of the hardened steel
marginally. However, this marginal loss is adequately compensated by advantages gained by
relieving of internal stresses, restoration of ductility and toughness and transformation of
retained austenite. The higher the tempering temperature, the more is the restored ductility and
tougher the steel. However, due attention should be paid towards hardness, strength and wear
resistance properties. This is the aim of hardening treatment. Proper tempering treatment
results in optimum combination of mechanical properties. Elastic properties of steel are also
affected by this treatment. Hardening followed by tempering is the only conventional heat
treatment process suitable for improving elastic limit of steel.

5.6.1 Structural Changes during Tempering

A number of structural changes take place during tempering treatment. These changes include
isothermal transformation of retained austenite, ejection of carbon from body centred tetragonal
lattice of martensite, growth and spheroidization of carbide particles and formation of ferrite-
carbide mixture. Depending on the range of tempering temperature, the treatment proceeds to
various stages.
The first stage of tempering is also referred to as low temperature tempering. The maximum
temperature to which steel is heated is restricted to about 250°C at this stage. This results in
 Heat Treatment Processes for Steels 101

the formation of a low carbon martensite and a carbide by transformation of high carbon
martensite. This decomposition of high carbon martensite proceeds essentially by nucleation
and growth. The carbon content of the product martensite (low carbon martensite) is
independent of the carbon content of the original martensite. Carbon content decreases with
increase in tempering time. It continues till the carbon of product martensite reaches a value
equal to 0.30 percent carbon. This amount of carbon in martensite leads to a stable state within
this temperature range and this martensite does not decompose further.
The carbide precipitated from the high carbon martensite during the first stage of tempering
is not cementite. This carbide is known as epsilon (e) carbide which has a hexagonal closed
packed structure. The carbon content of epsilon carbide is more than that of cementite (Fe3C),
and the chemical formula is approximately Fe2.4C. The carbon atoms are located at octahedral
interstices and arrange themselves in such a fashion that each one is separated from the other
with a maximum possible distance. Epsilon carbide forms at low temperature range in which
martensite is metastable. Hence, the carbide particles are very fine in size. The carbon contents
of the original martensite also affect the temperature range of formation of epsilon carbide.
As far as mechanical properties are concerned, marginal decrease in hardness value takes
place at this stage. Strength improves considerably. Toughness also improves but to a lesser
degree as compared to strength. Excellent wear resistance and reduced internal stresses are the
characteristics of hardened steel tempered in this range. The treatment is useful for high carbon
and low alloy steels used for manufacturing cutting and measuring tools. Case hardened steels
are also subjected to this treatment.
The second stage of tempering consists of heating steels in the temperature range varying
from 350 to 500°C. During this stage, retained austenite transforms to bainite. This bainite
differs from conventional bainite in the sense that it consists of ferrite and epsilon carbide.
Another name given to this stage is medium temperature tempering. Ductility and toughness
increase by this treatment with a corresponding decrease in hardness and strength. The steel
develops maximum elastic properties during this stage and the process is best suited for coil
and laminated springs.
The third stage of tempering is also popularly known as high temperature tempering. It
consists of heating steel within a temperature range of 500 to 680°C. Heating to such high
temperatures results in the formation of ferrite-cementite mixture. Martensite changes to ferrite
by losing its carbon. Carbon thus released combines with epsilon carbide which in turn
transforms to cementite. All these changes occur with the help of diffusion and nucleation.
Steel, thus treated, has better tensile, yield and impact strength than annealed or normalized
steel and is free from internal stresses. The process is best suited for medium carbon and
medium carbon low alloy steels due to their optimum heat treatment response. Connecting
rods, shafts and gears are frequently subjected to this treatment. Figure 5.7 shows the effect
of tempering temperature on hardness of quenched steel.

5.6.2 Effect of Alloying Elements on Tempering

Almost all alloying elements enhance the ability of steel to resist softening during tempering.
In other words, for a given hardness, alloy steels require higher tempering temperatures than
carbon steels. The same fact may be stated also for a given tempering cycle, i.e. an alloy steel
will have higher hardness than a plain carbon steel of same carbon content. It is not possible
102 Heat Treatment—Principles and Techniques

Figure 5.7 Effect of tempering temperature on the hardness of some quenched steels.

to derive a quantitative relationship between alloy content and the resistance to softening as
a number of variables are associated with the treatment. Alloy steels do not exhibit any
appreciable change in properties at low tempering temperatures, say up to 150°C.
Alloying elements can, in general, be classified into two classes, namely, carbide forming
elements and non-carbide forming elements such as nickel, aluminium, silicon and manganese,
which enter into ferrite and/or austenite. Thus, they have very little impact on the tempered
hardness of steel. The hardening observed in such alloy steels is essentially due to the solid
solution hardening effect. Steels with carbide forming elements, such as chromium, molybdenum,
tungsten, vanadium, tantalum and titanium, resist softening considerably because of the formation
of respective alloy carbides. Also, the martensite formed in alloy steels is much more stable.
The reason for this is that the martensite is formed from a highly alloyed austenite at lower
transformation temperatures. Lower transformation temperature is a consequence of lowered
Ms temperature due to the presence of alloying elements (see Section 4.9).
For some highly alloyed steels, improvement in hardness values has been observed on
tempering at elevated temperatures, which is contrary to the basic nature of tempering process.
Such a behaviour is referred to as secondary hardening. This hardening results from the
formation of alloy carbides. These alloy carbides are formed at higher temperatures and are
harder and more stable than cementite. Formation of cementite depends only on diffusion rates
of carbon, which is sufficiently high even at lower temperatures. Thus, cementite is easily
formed at lower temperatures. The reason why alloy carbides are formed only at higher
temperatures is the lower diffusion rates of alloying elements. The diffusion of solute atoms
is too slow at lower temperatures to cause any carbide formation. It is significant only at high
temperatures which permits formation of alloy carbides.

5.6.3 Temper Brittleness

One of the important objectives of tempering steel is to get an optimum combination of
strength and toughness. Since it is a subcritical treatment, cooling from tempering temperatures
 Heat Treatment Processes for Steels 103

can be done at any desired rate. It has been found that certain types of steels, either on
cooling slowly or on holding for prolonged periods within a specific tempering temperature
range (usually between 400°C and 660°C), show a marked decrease in toughness values. This
phenomenon is known as temper brittleness. Another name given to it is temper embrittlement.
The degree of embrittlement depends on the cooling rate from the embrittlement range. The
higher the rate of cooling, the lesser will be the degree of embrittlement. Many theories have
been put forward to explain this behaviour, but none can explain all the features associated
with it. However, some methods of commercial importance have been developed to reduce the
ill effect of temper embrittlement. An interesting feature of this embrittlement is that most of
the mechanical properties, such as hardness, tensile strength, yield strength, fatigue strength
and ductility as measured by percentage elongation, are not affected significantly. Temper
brittleness is a reversible phenomenon. It can be eliminated by heating steel above the
embrittlement range followed by rapid cooling.
Temper brittleness does not occur in carbon steel, but has been widely observed in alloy
steels. Steels with phosphorus, antimony, tin and arsenic are highly prone to this phenomenon.
The tendency is considerably reduced and practically eliminated in the absence of these
elements. This is the reason why it is emphasized that the presence of stray elements other than
those deliberately added should be carefully guarded against. This will ensure elimination of
embrittlement. If the presence of embrittlement elements is suspected, molybdenum, titanium
and zirconium are to be added so as to suppress embrittlement. Certain elements such as
nickel, manganese, chromium and silicon are also known to enhance the susceptibility of steel
to embrittlement.

5.6.4 Temper Colours

Hardened steel, when heated in oxidizing atmosphere for the purpose of tempering, exhibits
various colours on the surface. The colours are caused by the formation of iron oxide film. The
colour of oxide film is a function of oxide film thickness which, in turn, is a function of
tempering temperature and holding time at this temperature. As the oxide film thickness
increases, colour changes from light straw to grey. Table 5.1 indicates temper colour and
tempering temperatures.

Table 5.1 Temper Colours

Temperature Temper colours

(°C)
220 Straw yellow
240 Light brown
270 Brown
285 Purple
295 Dark blue
310 Light blue
325 Grey
350 Grey-purple
375 Grey-blue
400 Dull grey
104 Heat Treatment—Principles and Techniques

5.7 AUSTEMPERING

This is a special heat treatment process in which austenite is transformed into bainite. The
cooling sequence for austempering superimposed on TTT diagram is shown in Figure 5.8. In
general, austenite is either transformed
into pearlite or martensite during
conventional heat treatment processes
involving continuous cooling. The
nature of TTT diagram is such that a
given cooling curve cuts the C-curve
either above the nose or does not
intersect the curve at all. In the former
case, pearlite is formed. Martensite is
formed in the latter case. Austempering
consists of heating steel to above the
austenitizing temperature. It is then
quenched in a bath maintained at a
constant temperature above Ms point and
within the bainitic range (200 to 400°C,
in general). The steel is quenched and Figure 5.8 Cooling sequence for austempering
maintained at a constant temperature in treatment superimposed on TTT diagram.
the bath itself till all the austenite is
transformed into bainite. After complete transformation, steel is taken out of the bath and is
cooled in air or at any desired rate to room temperature. Since the process involves
transformation of austenite to bainite at constant temperature, it is also known as isothermal
quenching or isothermal hardening. The preferred temperature of the quenching bath is generally
on the lower side of bainitic range. This results in the formation of lower bainite which has
better mechanical properties than tempered martensite, and hence austempered components
rarely need tempering.
The process, as compared to conventional hardening and tempering treatment, results in
better ductility at high hardness levels, improved impact and fatigue strength and freedom
from distortion. Since bainite is formed at constant temperature, the properties of austempered
steels are uniform throughout the section. Two important parameters which control the process
are cooling rate for the first quench and holding time in the quenching bath. Steel must be
cooled at such a rate that austenite to pearlite transformation cannot take place. In other words,
the cooling rate has to be faster than the upper critical cooling rate. Thus, cooling rate imposes
restrictions on the steel composition and size. Limitation on size is necessary since the part is
required to attain uniform temperature of the quenching bath rapidly. Therefore, only
comparatively thin sections can be austempered successfully. The suitability of a given steel
for austempering can be determined with the help of TTT diagram. Only that steel, for which
austenite to pearlite transformation is comparatively slow, is suitable. The nose of the TTT
curve should be sufficiently away from the temperature axis. Also, the time required to complete
austenite to bainite transformation should be within reasonable limits. Very few alloy steels
fulfil these requirements.
 Heat Treatment Processes for Steels 105

5.8 MARTEMPERING

Similar to austempering, martempering

involves heating the steel to the austenitizing
temperature, followed by quenching in a
constant temperature bath maintained above
Ms point. The usual temperature of the bath
lies between 180°C and 250°C. Steel is held
in the bath till temperature throughout the
section becomes uniform and is equal to the
bath temperature. As soon as this temperature
is attained, steel is withdrawn and cooled in
air. The cooling rate should be sufficiently
high and holding time considerably short to
prevent transformation of austenite to pearlite
or to bainite. Martensite is formed in the Figure 5.9 Cooling sequence for martempering
second stage, namely, during cooling in air. treatment superimposed on TTT
The cooling sequence for martempering diagram.
superimposed on TTT diagram is shown in
Figure 5.9. Martempering results in minimum internal stresses, reduced tendency towards
distortion and cracking and improved mechanical properties as compared to conventional
quenching and tempering treatment. The resultant microstructure of martempered steel is
martensite. In order to improve properties, martempered steels are generally tempered.
Since the success of the process depends on the formation of martensite, alloy steels are
best suited for the process. Almost all alloying elements, except cobalt, increase hardenability.
Any steel, which can be hardened by oil quenching, can be martempered successfully. Smaller
sections of these steels which can only be hardened by water quenching can also be employed
for this process. A large number of steels satisfy these requirements. Another advantage of
using alloy steels is that alloying elements increase incubation period. This results in availability
of sufficient holding time.

5.9 SUB-ZERO TREATMENT

The resultant microstructure of a fully hardened steel should consist of martensite. In practice,
it is very difficult to have a completely martensitic structure by hardening treatment. Some
amount of austenite is generally present in the hardened steel. This austenite existing along
with martensite is referred to as retained austenite. Conventional metallography does not reveal
the presence of retained austenite till it exceeds 20 percent. The presence of retained austenite
greatly reduces mechanical properties and such steels do not develop maximum hardness even
after cooling at rates higher than the critical cooling rate. The amount of retained austenite
depends largely on the chemical composition of steel. For plain carbon steels, the amount of
retained austenite increases with the rise in carbon contents. Figure 4.32 shows the effect of
carbon on the amount of retained austenite. The problem of retained austenite is more complex
in alloy steels. Most of the alloying elements increase the content of retained austenite.